Method of preparing wrinkle compositions



- called wrinkling oils.

. blown drying oils, such as China-wood, linseed,

PatentedApr. 25, 1944 OF PREPARING WRINKLE comosrrions 7 METHOD l-lcl:

-William A. Waldie, Oakwood, Ohio, assignor to New Wrinkle, Inc., Dayton,

of Delaware Ohio, a corporation No Drawing. Original application December 5,

1941, Serial No. 421,769.

Divided and this application September 4, 1942, Serial No. 457,333

2 Claims. (01. 106-243) fatty acids (such as. China-wood oil fatty acids and linseed oil fatty acids or mixtures thereof) to varnish compositions, I can control the nature of the wrinkle finish produced upon drying of the varnish which has been modified by the addition of such oil fatty acids. Wrinkle finishes hitherto made have been compounded using. so-

Raw China-wood oil and perilla, oiticica, etc., are representative of these so-called wrinkling oils. I

Other paint and varnish oils, such as soya bean,

chia, walnut, hempseed, lumbang, poppy seed, sunflower seed, safliower seed, castor, fish, etc., which are classified as nonwrinkling oils have been used in admixture with wrinkling oils. However, large amounts of nonwrinkling oils cannot be used in the formulation of wrinkle finishes because they act as inhibitors in the formation of the desirable wrinkle finish. Prior to my present invention it has been necessary to use blown or pre-oxidized oils in compounding wrinkle finishes in order to obtain the most satisfactory results, and this was particularly true where wrinkle finishes o1 sprayable consistency were desired.

The use of blown oils presents certain disadvantages. Primarily, they are unstable; and this inherent instability is a result of the preoxidation treatment which they have undergone. It

appears that oxidation continues in a progressive manner after the end of the blowing treatment and this results in a change in the physical and chemical make-up thereof in storage.

Blown oils are characterized by their solubility in the conventional petroleum and coal tar solvents, but as auto-oxidation continues subsequent to the blowing treatment, they become increasingly less soluble and eventually precipitate 50 out as a rubber-like mass. This condition renders them unfit for usein wrinkle composition, and wrinkle finish coating compositions including blown oil constituents cannot be stored for any great length of time prior to use.

It is known, that wrinkle coating compositions including blown oils produce a wrinklefinish of coarse texture, and since the greatest demand is for wrinkle finishes having a fine, delicate texture, coating compositions including blown oils are not considered suitable.

The primary object of this invention is to produce wrinkle finish compositions which are stable on storage and may be, modified in order to control and vary at will the texture of the wrinkle pattern which they will produce on drying.

Another purpose of this invention is to produce such a coating composition without the use of blown oils but adapted to produce the fine, delicate wrinkle pattern or texture which is a characteristic of freshly made wrinkle finishes including blown oils.

The coating compositions produced according to the method of my invention may be controlled typical formula as follows:

Varnish "A-I Modified henol aldehyde resin (Ain- -bero or Beckacite") pounds 100 Lead acetate or linoleate do.. 5-9

Raw China-wood oil.- gallons 15-25 I Bodied linseed oil i do 2-5 Solvent naphtha do 8-10 Toluol do 18-25 Varnish ".4-2

Modified phenol aldehyde resin (Amberol or Beckacite") pounds 100 Lead acetate or linoleate do 5-9 40 Raw China-wood oil gallons 12-20 Bodied perilla oil do.. 5-10 Solvent naphtha do 8-10 Toluol i do 18-25 Varnish Ar-3 Modified phenol aldehyde resin (-Ambero orPBeckaclte") pounds Lead acetate or linoleate ..do 5-9 Raw China-wood oil gallons 5-10 Bodied oiticica do 12-20 Solvent naphtha do.. 8-10 Toluol do 18-2-5 In the foregoing varnish formulae the synthetic resins employedare of the oil soluble pheas nolaldehyde type, typicalformulae and method 1' employ a wrinkling varnish base having a of making which are shown in United States patents, 1,623,901 and 1,632,113.

It will be understood that various other resins may be utilized in place of those mentioned. Resins which are suitable are kauri, dammar, Congo, Cumar," pontianak, manila, Zanzibar, copal and the like. Furthermore, other phenol formaldehyde resins of the rosin modified, fossil resin modified and ester gum modified types,

' .which are readily compatible with the oil vehicle,

may be used. Also glycerol phthalic resins of the oil soluble type may be utilized, or mixtures of the above resins.

'Other wrinkling paint oils such as poyok, parinarium oils or equivalent oils containing oly-conjugated double bond linkage may be substituted for the wrinkling oils mentioned in the formula. The bodied linseed oil employed is the grade known in the trade as varnish linseed).

This product comprises linseed oil which has been processed by heat treating the same between 575 .to 600 F. until a desired degree of viscosity is obtained. Similarly the bodied perilla oil utilized has been bodied by heat treating in the same manner as in making bodied linseed oil. The .oiticica oil used has been bodied by heat treating at a temperature around 450 to 550 F. for an hour to an hour and a half.

The preferred method of making varnishes A-l, A-2" and "IL-3 is to heat all the Chinawood oil together with approximately V4 to /4 of the resin in a vessel to a temperature around 540 F. and hold them at or about that temperature for the desired viscosity increase of the oil, which viscosity might be that just short of incipient polymerization. Thereafter the metallic drier, remainder" of the oil and the resin are added. When the resin is dissolved the product can be cooled and thinned with solvent or it can be heated longer to obtain a higher viscosity before thinning.

I have discovered, however, that if the varnish is cooled quickly after the second portion of resin is dissolved, a clear wrinkle varnish can be made having improved spraying and wrinkling properties. The essential step in making varnishes A-l, ll-2" and A-3 is the sudden chilling or cooling of the heat treated oleoresinous mass immediately at the end of the heat treatment. This may be done in any suitable manner such as by the direct application of cold water or by refrigoration.

This method of making the varnish base composition makes it possible ultimately to obtain a sprayable wrinklefinish product which is comparable in texture with that made with blown oils and which does not have their disadvantage as regards instability on storing. The heat treatment in making the varnishes, it will be understood, may be varied between a temperature range of 450 to 550 F., depending upon the particular product desired, but preferably the heating is conducted above 500 F. a

By maintaining the percentage amount of the total solids in the composition the same and heating the product for different lengths of time, I

can regulate the viscosity of the varnish. The

the above varnishes A-l, A-2" or "ll-3 about 2 to 5 per cent of a liquid drier added to the var- 7 nishes. A' drier composition which has been found to be very satisfactory for this Purpo e is as follows:

Liquid drier "41 Cobalt linoleate solid pounds 12-16 China-wood oil fatty acids -do 8-10 Toluol, xylol, petroleum naphtha or coal tar solvent "gallons--. 6-8

Other examples of liquid driers which may be utilized are as follows:

Liquid drier B Lead linoleate -pounds 5-10 Cobalt acetate do 2-6 Linseed oil fatty acids do 2-5 China-wood oil fatty acids do 4-6 Toluol, xylol, petroleum naphtha or coal tar solvent gallons 6-8 Liquid drier "0 Lead linoleate pounds 4-8 Manganese boratee do 2-5 Cobalt acetate do 1-3 Drying oil fatty acids (China-wood oil, linseed, etc.) pounds 5-8 Toluol, xylol, petroleum naphtha or coal tar solvent pounds 6-9 Limited control of the textural pattern of the wrinkle finish obtained by mixing varnishes of the type of IL-1," A-2" and A-3 with liquid drier of the type of A, B or C may be had by controlling the viscosity of the mixture according to the Gardner-Holdt standards for varnish. In general, the higher the viscosity of the varnish, the coarser the texture of the wrinkle finish produced. I

It will be noted that the wrinkling varnish base such as typified by the formulations A-l," A-2 and A-3 is not per se a wrinkle composition and that in order to convert it into a wrinkle composition, it is necessary to add to it about 2 to 5 per cent of a liquid drier typified by the formulations for liquid driers A. 28" and C hereinbefore set forth. Such liquid drlers' may be added to the varnish base formulations A-l," A-2 and A-3" immediately following the addition of the solvent to the varnish, but when this is done and the mixture is stored at the plant, considerable loss may result from kinning. It is thus better practice to withhold the addition of. drier to the varnish base until it is ready for shipment.

According to my invention, however, I can control the texture of the wrinkle pattern of such a mixture and consistently produce a wrinkle finish characterized by ita'fine, delicate texture. This I do by adding to the mixture of varnish and drier a liquid texture modifier of which the following examples are typical:

Liquid texture modifier A china-wood oil fatty acids ..pounds-- 8-10 Hydrocarbon solvent-.. "gallons..- 1

, Liquid texture modifier "3 Linseed oil fatty acids pounds 2-5 China-wood oil fatty acids do 3-5 Hydrocarbon solvent "gallons" 1 By adding various proportions of these liquid texture modifiers to low viscosity varnishes such as "A-l," "IL-2" or "A-s including a liquid drier such as "A, "3 or "C." the texture or pattern of the wrinkle produced on drying is modified and may be accurately controlled and reproduced at will. The higher the proportion of liquid texture modifier added to the varnish-drier mixture, the finer will he the texture of the resulting wrinkle finish.

In drying the improved wrinkle finish of this invention, articles coated with the coating composition may be made to wrinkle by baking the coating at relatively low or high temperatures. For metallic and similar surfaces a temperature of 140 to 475 F. may be employed. For application of the coating on wood, paper and similar materials a somewhat lower temperature on the order of 125 to 150 F. may be used. Ordinarily baking the finish at elevated temperatures accentuates the wrinkling and provides a harder finish. Where a highly'elastic him is desired, the addition of small amounts oi nondrying or semidrying oils, such as castor oil, raw soya bean oil or similar materials may be made. Plasticizers such as dihutyl-phthalate or tricresyl phcsphatealso may be utilized.

The reason why the lead acetate or linoleate drier constituent does not suiiice to cause the varnish base A-l, "A-2 and A-3" to wrinkle is that lead driers are bottom driers while the formation of commercially valuable wrinkle finish requires also the use of "top driers." In essence, the mechanism of wrinkle formation is to cause rapid drying of the top surface or the him. This causes shrinkage, which is evidenced by wrinkle formation.

The cobalt-containing liquid driers "A," B and C" are characteristically "top driers and therefore, when they are incorporated with varnish base A-l, "A-2" and A-3" the resulting mixture constitutes awrinkle finish coating.

Thetextureorthemixtureotvarnishbaseand cobalt drier, however, is characterized by rather coarse wrinkles are undesirable for use in the higher types of work, and according to my invention I can change or modify the texture of the finish and produce the desirable fine wrinkles by the addition of various amounts oi! the liquid texture modifier of my invention.

Coating compositions made according to this invention are useful in the manufacture of vari- I ous compositions such as varnishes, enamels, linoleum, imitation leather and coatings for paper, metal and the like. Diflferent decorative effects can be produced by applying the wrinkling compositions and drying or baking them to a hard dry finish.

It will he understood that while I have described certain specific embodiments of my invention, I do not intend that it be limited to or circumscribed hy the specific details of procedure and proportions herein set forth in view of the tact that my invention may be modified according to individual preference and local conditions without departing from the spirit of this disclosure and the scope of the appended claims.

I claim:

1. In the method of manufacturing wrinkle coating compositions, the step comprising adding to a wrinkle varnish base including a bottom drier and a top drier, a texture modifyin a ent com rising a mixture oi. fatty acids oi linseed oil and China-wood oil and a solvent therefor.

2. In the method of manufacturing wrinkle coating compositions, the step comprising addin to a wrinkle varnish base including a bottom drier and a top drier, a texture modifying agent comprising hydrocarbon solvent and a mixture of fatty acids of linseed oil and China-wood oil.

' WILLIAM A. WALDIE. 

